U.S. patent application number 16/057091 was filed with the patent office on 2018-12-06 for 6-desoxy-6-amino-celluloses as soil release agents.
This patent application is currently assigned to Henkel AG & Co. KGaA. The applicant listed for this patent is Henkel AG & Co. KGaA. Invention is credited to Kristin Ganske, Thomas Heinze, Frank Janssen, Mareile Job, Christa Junkes, Christian Kropf, Anja von Kathen.
Application Number | 20180346846 16/057091 |
Document ID | / |
Family ID | 57956305 |
Filed Date | 2018-12-06 |
United States Patent
Application |
20180346846 |
Kind Code |
A1 |
Kropf; Christian ; et
al. |
December 6, 2018 |
6-DESOXY-6-AMINO-CELLULOSES AS SOIL RELEASE AGENTS
Abstract
Compositions and methods to improve the cleaning performance of
washing agents during laundering of textiles are disclosed.
Compositions described use 6-desoxy-6-amino-celluloses. Methods for
laundering textiles, in which a detergent and a soil release active
ingredient are used in the form of a cellulose derivative as
defined above, are also included. These methods can be performed
manually or as appropriate with the aid of a conventional domestic
washing machine.
Inventors: |
Kropf; Christian; (Hilden,
DE) ; Janssen; Frank; (Koeln, DE) ; Job;
Mareile; (Leverkusen, DE) ; Junkes; Christa;
(Duesseldorf, DE) ; von Kathen; Anja; (Wuppertal,
DE) ; Heinze; Thomas; (Jena, DE) ; Ganske;
Kristin; (Jena, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Henkel AG & Co. KGaA |
Duesseldorf |
|
DE |
|
|
Assignee: |
Henkel AG & Co. KGaA
Duesseldorf
DE
|
Family ID: |
57956305 |
Appl. No.: |
16/057091 |
Filed: |
August 7, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/EP2017/052188 |
Feb 2, 2017 |
|
|
|
16057091 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C11D 3/0036 20130101;
C11D 3/227 20130101 |
International
Class: |
C11D 3/22 20060101
C11D003/22; C11D 3/00 20060101 C11D003/00 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 2, 2016 |
DE |
102016202143.5 |
Claims
1. A detergent, containing a cellulose derivative comprising a
modified anhydroglucose unit of general formula I. ##STR00007## in
which the groups R stand independently of one another for H,
OR.sup.1, OC(O)R.sup.1, O(CH.sub.2).sub.nCOOX,
O(CH.sub.2).sub.nSO.sub.3X with n=1-4 or p-toluene sulfonate, and X
stands for H or an alkali metal ion, and R.sup.1 and R.sup.2 stand
independently of one another for --H, aryl groups, straight-chain
or branched alkyl, aryl, alkylaryl or arylalkyl groups, which can
be substituted with one or more functional groups, wherein the
aforesaid acids can also be present wholly or partially in salt
form, and/or in which a C atom or a plurality of non-adjacent C
atoms can be replaced by heteroatoms, to which they are bonded form
a 4 to 7-membered aliphatic or aromatic ring, which, besides the
aforesaid N atom, can also comprise one or more further
heteroatoms.
2. The detergent according to claim 1, wherein it comprises the
cellulose derivative in amounts of from 0.05 wt. % to 10 wt. %.
3. The detergent according to claim 1, wherein, in the general
formula I, R.sup.1 and R.sup.2 are selected, independently of one
another, from H, methyl, ethyl, propyl, isopropyl, ##STR00008##
(C.sub.2H.sub.4).sub.n--OH, --(C.sub.2H.sub.4).sub.n--OCH.sub.3,
--(C.sub.2H.sub.4).sub.n--OC.sub.2H.sub.5,
--(C.sub.3H.sub.6).sub.n--OH, --(C.sub.3H.sub.6O).sub.n--OCH.sub.3,
--(C.sub.3H.sub.60).sub.n--OC.sub.2H.sub.5 with, in each case, n=1
to 20, and mixtures thereof, or R.sup.1 and R.sup.2, together with
the N atom to which they are bonded, form a 5 to 6-membered
aliphatic ring, selected from tetrahydropyrrole, piperidine,
oxazolidine, morpholine, imidazolidine, piperazine, thiazolidine,
tetrahydro-1,4-thiazine, and mixtures thereof; and/or in that the
average degree of substitution based on the proportion of 6-amino
groups, in the cellulose derivative, lies in the range of from 0.1
to 1; and/or the average degree of substitution based on the
proportion of 2- or 3-tosyl groups, in the cellulose derivative, is
not more than 0.5.
4. A method for laundering textiles, comprising a step wherein a
detergent and a cellulose derivative comprising a modified
anhydroglucose unit of general formula I ##STR00009## in which the
groups R stand independently of one another for H, OR.sup.1,
OC(O)R.sup.1, O(CH.sub.2).sub.nCOOX, O(CH.sub.2).sub.nSO.sub.3X
with n=1-4 or p-toluene sulfonate, and X stands for H or an alkali
metal ion, and R.sup.1 and R.sup.2 stand independently of one
another for --H, aryl groups, straight-chain or branched alkyl,
aryl, alkylaryl or arylalkyl groups, which can be substituted with
one or more functional groups, wherein the aforesaid acids can also
be present wholly or partially in salt form, and/or in which a C
atom or a plurality of non-adjacent C atoms can be replaced by
heteroatoms, to which they are bonded form a 4 to 7-membered
aliphatic or aromatic ring, which, besides the aforesaid N atom,
can also comprise one or more further heteroatoms, is contacted
with textiles in a washing liquor.
5. The method according to claim 4, wherein the concentration at
which the cellulose derivative is used in the washing liquor is
0.0001 g/L to 1 g/L.
6. The method according to claim 5, wherein the concentration at
which the cellulose derivative is used in the washing liquor is
0.001 g/L to 0.2 g/L.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to the use of certain soil
release active ingredients for improving the cleaning performance
of detergents during laundering of textiles.
BACKGROUND OF THE INVENTION
[0002] In addition to the ingredients indispensable for the washing
process, such as surfactants and builder materials, detergents
generally also contain further constituents, which can be
summarized under the term washing auxiliaries and which comprise
active ingredient groups as diverse as those such as foam
regulators, anti-graying agents, bleaching agents, bleach
activators, and dye transfer inhibitors. Auxiliaries of this type
also include substances which give the laundry fibers
dirt-repelling properties and which, if present during the washing
process, support the dirt-repelling capability of the other
detergent constituents. The same is also true, analogously, for
cleaning products for hard surfaces. Dirt-repelling substances of
this type are often referred to as "soil release" active
ingredients or, on account of their ability to make the treated
surface, for example the fibers, dirt-repelling, are referred to as
"soil repellents". For example, the dirt-repelling effect of methyl
cellulose is known from US patent U.S. Pat. No. 4,136,038. European
patent application EP 0 213 729 discloses the reduced redeposition
with use of detergents that contain a combination of soap and
non-ionic surfactant with alkyl hydroxyalkyl cellulose. Textile
treatment agents which contain cationic surfactants and non-ionic
cellulose ethers with HLB values of from 3.1 to 3.8 are known from
European patent application EP 0 213 730. US patent specification
U.S. Pat. No. 4,000,093 discloses detergents that contain 0.1 wt. %
to 3 wt. % of alkyl cellulose, hydroxyalkyl cellulose, or alkyl
hydroxyalkyl cellulose, and 5 wt. % to 50 wt. % of surfactant,
wherein the surfactant component consists substantially of C.sub.10
to C.sub.13 alkyl sulfate and up to 5 wt. % of C.sub.14 alkyl
sulfate, and less than 5 wt. % of alkyl sulfate with alkyl groups
of C.sub.15 and higher.
[0003] Due to their chemical similarity to polyester fibers,
particularly effective soil release active ingredients in textiles
made of this material are copolyesters containing dicarboxylic acid
units, such as terephthalic acid or sulfoisophthalic acid, alkylene
glycol units, such as ethylene glycol or propylene glycol, and
polyalkylene glycol units, such as polyethylene glycol. Soil
release copolyesters of the aforesaid type and use thereof in
detergents have long been known.
[0004] The polymers known from the prior art have the disadvantage
that they do not have any efficacy, or have only inadequate
efficacy in particular in textiles that are not made of polyester,
or are not made primarily of polyester. A large amount of modern
textiles, however, are made of cotton or cotton-polyester blended
fabrics, and there is thus a need for soil release active
ingredients that have improved efficacy in particular in the case
of grease stains in particular on textiles of this kind.
[0005] It has surprisingly been found that this problem can be
solved by the use of certain cellulose derivatives.
[0006] International patent application WO 00/18860 A1 discloses
the rebuilding effect of what are called cellulose esters in that
document, which can also be cellulose carbamates, on textiles. This
is supposedly based on the fact that the cellulose esters are
deposited on the damaged textile areas, react with the fibers by
cleaving of the reactive ester functionality, and thus strengthen
the damaged areas by cellulose. It is known from international
patent application WO 00/18861 A1 that cellulose esters of this
kind increase the affinity of material to be deposited on a
substrate, such as a fiber, for said substrate. International
patent application WO 01/72937 A1 relates to the reduction of dye
losses when laundering dyed textiles by virtue of the use of
cellulose esters of this kind. International patent application WO
01/72944 A1 discloses the suitability of cellulose ethers of this
kind to increase the deposition of fragrances on textiles, and it
is known from patent application GB 2 360 791 A that they
contribute to fabric softness by virtue of their deposition on
textiles.
BRIEF SUMMARY OF THE INVENTION
[0007] The subject of the invention is the use of cellulose
derivatives that contain a modified anhydroglucose unit of general
formula I
##STR00001##
in which the groups R stand independently of one another for H,
OR.sup.1, OC(O)R.sup.1, O(CH.sub.2).sub.nCOOX,
O(CH.sub.2).sub.nSO.sub.3X with n=1-4 or p-toluene sulfonate, and X
stands for H or an alkali metal ion, and R.sup.1 and R.sup.2 stand
independently of one another for --H, aryl groups, straight-chain
or branched alkyl, aryl, alkylaryl or arylalkyl groups, which can
be substituted with one or more functional groups, in particular
hydroxy groups, carboxylic acid groups and/or sulfonic acid groups,
wherein the aforesaid acids can also be present wholly or partially
in salt form, and/or in which a C atom or a plurality of
non-adjacent C atoms can be replaced by heteroatoms, such as N, O
or S, or R.sup.1 and R.sup.2 together with the N atom to which they
are bonded form a 4 to 7-membered aliphatic or aromatic ring,
which, besides the aforesaid N atom, can also comprise one or more
further heteroatoms, such as N, O or S, to enhance the cleaning
performance of detergents during the laundering of textiles.
[0008] 6-desoxy-6-amino celluloses are accessible by known
production methods, for example by a two-stage synthesis consisting
of the conversion of cellulose with p-toluene sulfonic acid
chloride, as described in Angew. Makromol. Chem. [Appl. Macromol.
Chem.] 238 (1996) 143-163, into cellulose tosylates and subsequent
aminolysis of the tosylates with amines of the H--NR.sup.1R.sup.2
type to give the corresponding 6-amino-6-amino-cellulose
derivatives. Any tosyl groups still present can then be removed
hydrolytically wholly or at least in part (which leads to compounds
that contain groups with R.dbd.OH) or by substitution with hydride
ions (which leads to compounds that contain groups with R.dbd.H),
in particular if the reaction of the first stage led to tosylations
at positions other than at the OH group in position 6 of the
cellulose anhydroglucose units. If it is not cellulose that is used
as starting material, but instead correspondingly substituted
cellulose, compounds of general formula (I) with R.noteq.H and
R.noteq.OH are obtainable analogously, these can also be obtained
from the cellulose tosylate produced after the first-mentioned step
above and reaction of the free OH groups thereof with alkylation or
esterification reagents in the known manner. Modified
anhydroglucose units of general formula I are preferably those in
which R.sup.1 and R.sup.2 are selected, independently of one
another, from H, methyl, ethyl, propyl, isopropyl,
##STR00002##
--(C.sub.2H.sub.4O).sub.n--H, --(C.sub.2H.sub.4O).sub.n--CH.sub.3,
--(C.sub.2H.sub.4O).sub.n--C.sub.2H.sub.5,
--(C.sub.3H.sub.6O).sub.n--H, --(C.sub.3H.sub.6O).sub.n--CH.sub.3,
--(C.sub.3H.sub.6O).sub.n--C.sub.2H.sub.5 with, in each case, n=1
to 20, in particular 2 to 10, and mixtures thereof. In preferred
units of general formula I, R.sup.1.dbd.H and R.sup.2.noteq.H.
Preferred groups --NR.sup.1R.sup.2 also derive from amino alcohols,
such as 2-aminoethanol, 3-aminopropanol, 2-(2-aminoethoxy)ethanol,
N-2-(2-hydroxyethyl)ethylene diamine, (2-methoxyethyl)methylamine,
(2-ethoxyethyl)methylamine, 2-amino-1,3-propanediol,
2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol,
tris-(hydroxymethyl)aminomethane, N-aminomorpholine,
N-aminoalkyl-morpholine, polyalkoxylated and in particular
ethoxylated amines, aniline, which can be substituted at the ring
as desired, benzylamine, which can be substituted at the ring as
desired, such as p-aminobenzylamine, and mixtures thereof.
Preferred groups --NR.sup.1R.sup.2, in which R.sup.1 and R.sup.2,
together with the N atom to which they are bonded, form a 4 to
7-membered aliphatic or aromatic ring, in particular a 5 or
6-membered ring, derive from tetrahydropyrrole, piperidine,
oxazolidine, morpholine, imidazolidine, piperazine, thiazolidine,
tetrahydro-1,4-thiazine, and mixtures thereof. Particularly
preferred groups R.sup.1 and/or R.sup.2 include methyl, ethyl,
propyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-methoxyethyl,
2-ethoxyethyl,
##STR00003##
and mixtures thereof.
[0009] Besides the modified anhydroglucose unit of general formula
I, the cellulose derivative to be used in accordance with the
invention contains anhydroglucose units linked
1,4-.beta.-glycosidically therewith, which are free from the
6-desoxy-6-amino modification and which can be unsubstituted or
likewise modified such that they correspond to general formula I
apart from the absent 6-desoxy-6-amino modification. If desired, as
in the units of formula (I), O-substituents in the anhydroglucose
units free from 6-amino substituents can also carry R.sup.1 and/or
R.sup.2, which include, for example, alkyl groups, such as methyl
or ethyl groups, hydroxyalkyl groups, such as hydroxyethyl or
hydroxypropyl groups, or oligoethoxyethyl or oligopropoxypropyl
groups, carboxyalkyl groups, such as carboxymethyl or carboxyethyl
groups, aminoalkyl groups, such as aminoethyl or
trimethylammoniumethyl groups, sulfoalkyl groups, such as
sulfoethyl or sulfopropyl groups, ester groups, such as acetic
acid, .beta.-aminopropionic acid, glycolic acid, malonic acid or
p-toluene sulfonic acid ester groups. The average degree of
substitution based on the proportion of 6-amino groups
(DS.sub.amine) in the cellulose derivative to be used in accordance
with the invention lies preferably in the range of from 0.1 to 1,
in particular 0.2 to 0.8. The average degree of substitution based
on the proportion of 2- or 3-tosyl groups (DS.sub.tosyl) in the
cellulose derivative to be used in accordance with the invention
preferably does not lie above 0.5, in particular in the range of
from 0 to 0.25. If substituents at O atoms of the anhydroglucose
units are present, the average degree of substitution, based on the
proportion of groups of this kind, lies preferably beneath 1 and in
particular beneath the degree of substitution for the
6-desoxy-6-amino groups. In embodiments of the invention there are
no modifications contained in the cellulose derivative to be used
in accordance with the invention going beyond the introduction of
the 6-desoxy-6-amino group and, as applicable, of the tosylate
group.
[0010] A further subject of the invention is a method for
laundering textiles, in which a detergent and a soil release active
ingredient are used in the form of a cellulose derivative as
defined above. These methods can be performed manually or as
appropriate with the aid of a conventional domestic washing
machine. Here, it is possible to apply the detergent and the soil
release active ingredient at the same time or one after the other.
Application at the same time can be implemented particularly
advantageously by use of a detergent containing the soil release
active ingredient. The method relies fundamentally in bringing a
textile requiring cleaning or at least the soiled part of the
surface thereof into contact with an aqueous preparation containing
the above-defined cellulose derivative, leaving the aqueous
preparation to act for a certain time on the textile or at least
the soiled part of the surface thereof, and removing the aqueous
preparation, for example by rinsing the textile with water.
[0011] The effect of the active ingredient to be used in accordance
with the invention is particularly pronounced with multiple
application, that is to say in particular for the removal of stains
on textiles that had already been washed and/or aftertreated in the
presence of the active ingredient before they became stained. In
conjunction with the aftertreatment, it should be noted that the
referenced positive aspect can also be provided by a washing
process in which the textile, after the actual washing process,
which is performed with the aid of a detergent which can contain an
active ingredient as described, but in this case can also be free
from such an active ingredient, is brought into contact with a
aftertreatment agent, for example within the scope of a fabric
softening step, containing an active ingredient that is to be used
in accordance with the invention, in the presence of water. In the
case of this approach as well, the washing-performance-enhancing
effect of the active ingredients to be used in accordance with the
invention is provided during the next washing process, even if once
again a detergent without an active substance to be used in
accordance with the invention is used as desired. This effect is
much greater than achieved with use of a conventional soil release
active ingredient. In a particularly preferred embodiment, the
active ingredient essential to the invention is added in the fabric
softening process of the textile laundering, performed in
particular by machine.
[0012] The active ingredient used in accordance with the invention
leads to a significantly improved detachment in particular of
greasy and cosmetic stains on textiles, in particular on textiles
produced from cotton or cotton-containing fabric, compared to that
achieved with use of compounds known previously for this purpose.
Alternatively, with constant grease-removing capability,
significant amounts of surfactants can be spared.
[0013] In addition, it has been observed that, in the presence of
the cellulose derivatives essential to the invention in the
laundering process, there is a lower redeposition of dirt already
removed from the textile on the cleaned textile, and therefore the
textiles washed in the presence of a cellulose derivative are
essential to the invention become grayed to a much lesser extent
than those washed in the absence of the cellulose derivative
essential to the invention. A further subject of the invention is
therefore the use of the above-defined cellulose derivatives in
order to reduce the graying of textiles during laundering.
[0014] The uses according to the invention can be provided within
the scope of a laundering process, in such a way that the soil
release active ingredient is added to a detergent-containing
washing liquor or preferably introduces the active ingredient as
part of a detergent into the washing liquor, which contains the
item to be cleaned or is brought into contact therewith. Further
subjects of the invention are therefore detergents containing the
above-defined cellulose derivatives.
[0015] The use according to the invention within the scope of a
laundry aftertreatment process can be implemented accordingly in
such a way that the soil release active ingredient is added
separately to the rinsing water, which is used after the washing
process performed with application of a detergent, or it is
introduced as part of the laundry aftertreatment agent, in
particular a fabric softener. In this aspect of the invention, the
detergent used before the laundry aftertreatment agent can also
contain an active ingredient to be used in accordance with the
invention, but can also be free therefrom.
[0016] The washing process is preferably performed at a temperature
of from 15.degree. C. to 60.degree. C., particularly preferably at
a temperature of from 20.degree. C. to 40.degree. C. The washing
process is also preferably performed at a pH value of from 6 to 11,
particularly preferably at a pH value of from 7.5 to 9.5. The
concentration at which the cellulose derivative is used in the
washing liquor is preferably 0.0001 g/L to 1 g/L, in particular
0.001 g/L to 0.2 g/L.
[0017] Products that contain an active ingredient to be used in
accordance with the invention in the form of the described
cellulose derivative or which are used together therewith or are
employed in methods according to the invention can contain all
conventional other constituents of products of this kind which do
not interact undesirably with the active ingredient essential to
the invention, in particular surfactant. The above-defined active
ingredient is preferably used in amounts of from 0.05 wt. % to 10
wt. %, particularly preferably from 0.2 wt. % to 3 wt. %, wherein
these and amounts specified further below relate to the product as
a whole, unless specified otherwise.
[0018] It has surprisingly been found that the active ingredient
used in accordance with the invention positively influences the
effect of certain other detergent ingredients and that, conversely,
the effect of the soil release active ingredient is additionally
enhanced by certain other detergent ingredients. These effects are
observed in particular in the case of bleaching agents, in
enzymatic active ingredients, in particular proteases and lipases,
in water-soluble inorganic and/or organic builders, in particular
based on oxidized carbohydrates or polymer polycarboxylates, in
synthetic anion surfactants of the sulfate and sulfonate type, and
in dye transfer inhibitors, for example vinylpyrrolidone,
vinylpyridine, or vinylimidazole polymers or copolymers or
corresponding polybetaines, and therefore the use of at least one
of the aforesaid further ingredients together with the active
ingredient to be used in accordance with the invention is
preferred.
[0019] A product that contains an active ingredient to be used in
accordance with the invention or that is used together therewith or
that is used in the method according to the invention preferably
contains bleaching agent based on peroxygen, in particular in
amounts ranging from 5 wt. % to 70 wt. %, and as appropriate bleach
activator, in particular in amounts ranging from 2 wt. % to 10 wt.
%, but in another preferred embodiment can also be free from
bleaching agent and bleach activator. The bleaching agents under
consideration are preferably the peroxygen compounds generally used
in detergents, such as percarboxylic acids, for example dodecane
diperacid or phthaloylaminoperoxicaproic acid, hydrogen peroxide,
alkaliperborate, which can be present as tetra- or monohydrate,
percarbonate perpyrophosphate and persilicate, which generally are
present in the form of alkali salts, in particular in the form of
sodium salts. Bleaching agents of this type are contained in
detergents containing an active ingredient used in accordance with
the invention, preferably in amounts of up to 25 wt. %, in
particular up to 15 wt. %, and particularly preferably from 5 wt. %
to 15 wt. %, in each case in relation to the total product, wherein
percarbonate is used in particular. The optionally present
component of the bleach activators comprises the usually used N- or
O-acyl compounds, for example multiple acylated alkylene diamines,
in particular tetraacetylethylene diamine, acylated glycolurils, in
particular tetracetylglycoluril, N-acylated hydantoins, hydracids,
triazoles, urazoles, diketopiperazines, sulfuryl amides, and
cyanurates, additionally carboxylic acid anhydrides, in particular
phthalic acid anhydride, carboxylic acid esters, in particular
sodium isononanoyl phenol sulfonate, and acylated sugar
derivatives, in particular pentaacetyl glucose, and also cationic
nitrile derivatives, such as trimethylammonium acetonitrile salts.
The bleach activators may have been coated in the known manner with
enveloping substances in order to prevent interaction with the
peroxygen compounds during storage, and/or may have been
granulated, wherein tetraacetylethylenediamine granulated with the
aid of carboxymethyl cellulose and having average particle sizes of
from 0.01 mm to 0.8 mm, granulated
1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine and/or trialkyl
ammonium acetonitrile in particle form is particularly preferred.
Bleach activators of this type are contained in detergents
preferably in amounts of up to 8 wt. %, in particular from 2 wt. %
to 6 wt. %, in each case in relation to the total product.
[0020] In a preferred embodiment a product used in accordance with
the invention or employed in the method according to the invention
contains non-ionic surfactant, selected from fatty alkyl
polyglycosides, fatty alkyl polyalkoxylates, in particular
ethoxylates and/or propoxylates, fatty acid polyhdroxy amides
and/or ethoxylation and/or propoxylation products of fatty alkyl
amines, vicinal diols, fatty acid alkyl esters and/or fatty acid
amides and mixtures thereof, in particular in an amount ranging
from 2 wt. % to 25 wt. %.
[0021] A further embodiment of products of this kind comprises the
presence of synthetic anionic surfactant of the sulfate and/or
sulfonate type, in particular fatty alkyl sulfate, fatty alkyl
ether sulfate, sulfofatty acid esters and/or sulfofatty acid
disalts, in an amount ranging from 2 wt. % to 25 wt. %. The anionic
surfactant is preferably selected from the alkyl or alkenyl
sulfates and/or the alkyl or alkenyl ether sulfates, in which the
alkyl or alkenyl group has 8 to 22, in particular 12 to 18 C atoms.
These are not usually individual substances, but cuts or mixtures.
Those of which the proportion of compounds having longer-chain
groups ranging from 16 to 18 C atoms is more than 20 wt. % are
preferred.
[0022] Potential non-ionic surfactants include the alkoxylates, in
particular the ethoxylates and/or propoxylates of saturated or
mono- to polyunsaturated linear or branch-chained alcohols having
10 to 22 C atoms, preferably 12 to 18 C atoms. Here, the degree of
alkoxylation of the alcohols is generally between 1 and 20,
preferably between 3 and 10. They can be produced in the known
manner by reacting the corresponding alcohols with the
corresponding alkylene oxides. In particular, the derivatives of
the fatty alcohols are suitable, although the branch-chained
isomers thereof, in particular what are known as oxoalcohols, can
also be used for the preparation of usable alkoxylates.
Accordingly, the alkoxylates, in particular the ethoxylates, of
primary alcohols with linear, in particular dodecyl, tetradecyl,
hexadecyl or octadecyl groups as well as mixtures thereof can be
used. In addition, appropriate alkoxylation products of
alkylamines, vicinal diols, and carboxylic acid amides which
correspond in terms of the alkyl part to the specified alcohols can
be used. In addition, the ethylene oxide and/or propylene oxide
insertion products of fatty acid alkyl esters and also fatty acid
polyhydroxyamides can be considered. So-called `alkyl
polyglycosides` suitable for incorporation into the products
according to the invention are compounds of general formula
(G).sub.n-OR.sup.12, in which R.sup.12 means an alkyl or alkenyl
group having 8 to 22 C atoms, G means a glucose unit, and n means a
number between 1 and 10. The glycoside component (G).sub.n is
composed of oligomers or polymers from naturally occurring aldose
or ketose monomers, including in particular glucose, mannose,
fructose, galactose, talose, gulose, altrose, allose, idose,
ribose, arabinose, xylose and lyxose. The oligomers consisting of
glycosidically linked monomers of this type are additionally
characterized by the type of sugars contained therein, by the
number thereof, and by what is known as the degree of
oligomerization. The degree of oligomerization n generally assumes
fractional numerical values as a variable that is to be determined
analytically; it lies at values between 1 and 10, at which
glycosides used with preference are below a value of 1.5, in
particular between 1.2 and 1.4. A preferred monomer unit is glucose
due to the good availability. The alkyl or alkenyl part R.sup.12 of
the glycosides preferably also originates from easily accessible
derivatives of renewable raw materials, in particular from fatty
alcohols, although the branch-chained isomers thereof, in
particular what are known as oxoalcohols, can also be used for the
preparation of usable glycosides. In particular, the primary
alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl
or octadecyl groups and also mixtures thereof can be used
accordingly. Particularly preferred alkylglycosides contain a
coconut oil alkyl group, that is to say mixtures with substantially
R.sup.12=dodecyl and R.sup.12=tetradecyl.
[0023] Non-ionic surfactant is used in products that contain a soil
release active ingredient used in accordance with the invention,
that are used in accordance with the invention or that are employed
in the method according to the invention, preferably in amounts of
from 1 wt. % to 30 wt. %, in particular from 1 wt. % to 25 wt. %,
wherein amounts in the upper part of this range tend to be
encountered in liquid detergents, whereas particulate detergents
preferably tend to contain lower amounts of up to 5 wt. %.
[0024] The products can contain further surfactants instead or
additionally, preferably synthetic anionic surfactants of the
sulfate or sulfonate type, such as alkylbenzene sulfonates, in
amounts of preferably not more than 20 wt. %, in particular from
0.1 wt. % to 18 wt. %, in each case in relation to the product as a
whole. The alkyl and/or alkenyl sulfates having 8 to 22 C atoms
which carry an alkali-, ammonium- or alkyl- or
hydroxyalkyl-substituted ammonium ion as counter-cation can be
cited as synthetic anionic surfactants particularly suitable for
use in products of this type. The derivatives of the fatty alcohols
having in particular 12 to 18 C atoms and the branch-chained
analogues thereof, or what are known as the oxoalcohols, are
preferred. The alkyl and alkenyl sulfates can be produced in the
known manner by reacting the corresponding alcohol components with
a conventional sulfation reagent, in particular sulfur trioxide or
chlorosulfonic acid, and subsequent neutralization with alkali-,
ammonium-, or alkyl- or hydroxyalkyl-substituted ammonium bases.
The usable surfactants of the sulfate type also include the
sulfated alkoxylation products of the specified alcohols, or what
are known as ether sulfates. Ether sulfates of this type preferably
contain 2 to 30, in particular 4 to 10 ethylene glycol groups per
molecule. The suitable anionic surfactants of the sulfonate type
include the .alpha.-sulfoesters obtainable by reacting fatty acid
esters with sulfur trioxide and by subsequent neutralization, in
particular the sulfonation products deriving from fatty acids
having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear
alcohols having 1 to 6 C atoms, preferably 1 to 4 C atoms, and also
the sulfofatty acids arising from these as a result of formal
saponification.
[0025] Soaps can be considered as further optional surfactant
ingredients, wherein saturated fatty acid soaps, such as salts of
lauric acid, myristic acid, palmitic acid or stearic acid, and also
soaps derived from natural fatty acid mixtures, for example
coconut, palm kernel or tallow fatty acids, are suitable. In
particular, soap mixtures which are composed to an extent of up to
50 wt. % to 100 wt. % of saturated C.sub.12-C.sub.15 fatty acid
soaps and up to 50 wt. % of oleic acid soaps are preferred. Soap is
preferably contained in amounts of from 0.1 wt. % to 5 wt. %.
However, higher soap amounts of generally up to 20 wt. % can also
be contained in particular in liquid products containing a polymer
used in accordance with the invention.
[0026] If desired, the products can also contain betaine
surfactants and/or cationic surfactants, which, if present, are
preferably used in amounts of from 0.5 wt. % to 7 wt. %. Among
these, the esterquats discussed below are particularly
preferred.
[0027] In a further embodiment the product contains water-soluble
and/or water-insoluble builder, in particular selected from alkali
aluminosilicate, crystalline alkali silicate with modulus greater
than 1, monomeric polycarboxylate, polymeric polycarboxylate, and
mixtures thereof, in particular in amounts ranging from 2.5 wt. %
to 60 wt. %.
[0028] The product preferably contains 20 wt. % to 55 wt. % of
water-soluble and/or water-insoluble, organic and/or inorganic
builder. In particular, water-soluble organic builder substances
include those from the class of polycarboxylic acids, in particular
citric acid and sugar acids, and also the polymeric
(poly)carboxylic acids, in particular the polycarboxylates
accessible by oxidation of polysaccharides, polymeric acrylic
acids, methacrylic acids, maleic acids, and mixed polymers thereof,
which can also contain, polymerized therein, small proportions of
polymerizable substances without carboxylic acid functionality. The
relative molecular mass of the homopolymers of unsaturated
carboxylic acids generally lies between 5,000 g/mol and 200,000
g/mol, and that of the copolymers between 2,000 g/mol and 200,000
g/mol, preferably 50,000 g/mol to 120,000 g/mol, in relation to
free acid. A particularly preferred acrylic acid-maleic acid
copolymer has a relative molecular mass of from 50,000 g/mol to
100,000 g/mol. Suitable, although less preferred compounds of this
class are copolymers of acrylic acid or methacrylic acid with vinyl
ethers, such as vinyl methyl ethers, vinyl esters, ethylene,
propylene and styrene, in which the proportion of the acid is at
least 50 wt. %. Terpolymers which contain, as monomers, two
carboxylic acids and/or salts thereof and which contain, as third
monomer, vinyl alcohol and/or a vinyl alcohol derivative or a
carbohydrate can also be used as water-soluble organic builder
substances. The first acid monomer or salt thereof derives from a
monoethylenically unsaturated C.sub.3-C.sub.8 carboxylic acid and
preferably from a C.sub.3-C.sub.4 monocarboxylic acid, in
particular from (meth)acrylic acid. The second acid monomer or salt
thereof can be a derivative of a C.sub.4-C.sub.8 dicarboxylic acid,
wherein maleic acid is particularly preferred. The third monomer
unit is in this case formed by vinyl alcohol and/or preferably an
esterified vinyl alcohol. In particular, vinyl alcohol derivatives
which constitute an ester formed of short-chain carboxylic acids,
for example C.sub.1-C.sub.4 carboxylic acids, with vinyl alcohol
are preferred. Preferred terpolymers here contain 60 wt. % to 95
wt. %, in particular 70 wt. % to 90 wt. % of (meth)acrylic acid
and/or (meth)acrylate, particularly preferably acrylic acid and/or
acrylate, and maleic acid and/or maleinate and also 5 wt. % to 40
wt. %, preferably 10 wt. % to 30 wt. % of vinyl alcohol and/or
vinyl acetate. Here, terpolymers in which the ratio by weight of
(meth)acrylic acid and/or (meth)acrylate to maleic acid and/or
maleate is between 1:1 and 4:1, preferably between 2:1 and 3:1 and
in particular 2:1 and 2.5:1 are very particularly preferred. Here,
both the amounts and the ratios by weight are based on the acids.
The second acid monomer or salt thereof can also be a derivative of
an allylsulfonic acid which in the 2 position is substituted with
an alkyl group, preferably with a C.sub.1-C.sub.4 alkyl group, or
an aromatic group that derives preferably from benzene or benzene
derivatives. Preferred terpolymers here contain 40 wt. % to 60 wt.
%, in particular 45 to 55 wt. % of (meth)acrylic acid and/or
(meth)acrylate, particularly preferably acrylic acid and/or
acrylate, 10 wt. % to 30 wt. %, preferably 15 wt. % to 25 wt. % of
methallylsulfonic acid and/or methallysulfonate, and, as third
monomer, 15 wt. % to 40 wt. %, preferably 20 wt. % to 40 wt. % of a
carbohydrate. This carbohydrate here can be a mono-, di-, oligo- or
polysaccharide for example, wherein mono-, di- or oligosaccharides
are preferred, with sucrose being particularly preferred. Due to
the use of the third monomer, predetermined breaking points should
be incorporated in the polymer and are responsible for the good
biological degradability of the polymer. These terpolymers
generally have a relative molecular mass between 1,000 g/mol and
200,000 g/mol, preferably between 3,000 g/mol and 10,000 g/mol.
They can be used in the form of aqueous solutions, preferably in
the form of 30 to 50 wt. % aqueous solutions, in particular for the
production of liquid products. All specified polycarboxylic acids
are generally used in the form of their water-soluble salts, in
particular their alkali salts.
[0029] Organic builder substances of this type are preferably
contained in amounts of up to 40 wt. % in particular up to 25 wt.
%, and particularly preferably from 1 wt. % to 5 wt. %. Amounts
close to the specified upper limits are preferably used in pasty or
liquid, in particular water-containing products.
[0030] In particular, crystalline or amorphous alkali
aluminosilicates are used as water-insoluble, water-dispersible
inorganic builder materials, in amounts of up to 50 wt. %,
preferably not more than 40 wt. %, and in liquid products are used
in particular from 1 wt. % to 5 wt. %. Among these, the crystalline
aluminosilicates of detergent quality, in particular zeolite NaA
and optionally NaX, are preferred. Amounts close to the specified
upper limits are preferably used in solid, particulate products.
Suitable aluminosilicates in particular have no particles having a
particle size of more than 30 m and preferably consist to an extent
of at least 80 wt. % of particles having a size of less than 10
.mu.m. Their calcium bonding capability, which can be determined in
accordance with the details in German patent application DE 24 12
837, lies in the range of from 100 to 200 mg of CaO per gram.
Suitable substitutes or partial substitutes for the specified
aluminosilicate are crystalline alkali silicates, which can be
present alone or mixed with amorphous silicates. The alkali
silicates usable in the products as builder substances preferably
have a molar ratio of alkali oxide to SiO.sub.2 of less than 0.95,
in particular from 1:1.1 to 1:12 and can be present in amorphous or
crystalline form. Preferred alkali silicates are the sodium
silicates, in particular the amorphous sodium silicates, with a
molar ratio of Na.sub.2O:SiO.sub.2 of from 1:2 to 1:2.8. Such
amorphous alkali silicates are commercially obtainable for example
under the name Portil.RTM.. They are added preferably as a solid
and not in the form of a solution within the scope of the
production process. Crystalline sheet silicates of general formula
Na.sub.2SixO.sub.2x+1.yH.sub.2O, in which x, or what is known as
the modulus, is a number from 1.9 to 4 and y is a number from 0 to
20 and preferred values for x are 2, 3 or 4, are preferably used as
crystalline silicates, which can be present alone or mixed with
amorphous silicates. Preferred crystalline sheet silicates are
those in which x in the specified general formula assumes the
values 2 or 3. In particular, both .beta.- and .delta.-sodium
disilicates (Na.sub.2Si.sub.2O.sub.5.yH.sub.2O) are preferred.
Practically anhydrous, crystalline alkali silicates of the
above-mentioned general formula in which x means a number from 1.9
to 2.1 produced from amorphous alkali silicates can also be used in
products which contain an active ingredient to be used in
accordance with the invention. In a further preferred embodiment of
products according to the invention, a crystalline sodium sheet
silicate having a modulus of from 2 to 3 is used, as can be
produced from sand and soda. Crystalline sodium silicates having a
modulus ranging from 1.9 to 3.5 are used in a further preferred
embodiment of detergents containing an active ingredient used in
accordance with the invention. The content thereof of alkali
silicates is preferably 1 wt. % to 50 wt. %, and in particular 5
wt. % to 35 wt. %, in relation to anhydrous active substance. If
alkalialuminosilicate, in particular zeolite, is provided as
additional builder substance, the content of alkali silicate is
preferably 1 wt. % to 15 wt. % and in particular 2 wt. % to 8 wt.
%, in relation to anhydrous active substance. The ratio by weight
of aluminosilicate to silicate, in each case in relation to
anhydrous active substances, is then preferably 4:1 to 10:1. In
products that contain both amorphous and crystalline
alkalisilicates, the ratio by weight of amorphous alkalisilicate to
crystalline alkalisilicate is preferably 1:2 to 2:1 and in
particular 1:1 to 2:1.
[0031] In addition to the mentioned inorganic builder, further
water-soluble or water-insoluble inorganic substances can be
contained in the products that contain an active ingredient to be
used in accordance with the invention, that are used together
therewith, or that are employed in methods according to the
invention. In this context, the alkali carbonates, alkali hydrogen
carbonates, and alkali sulfates and mixtures thereof are suitable.
Additional inorganic material of this type can be provided in
amounts up to 70 wt. %.
[0032] In addition, the products can contain further constituents
that are conventional in detergents or cleaning products. These
optional constituents include in particular enzymes, enzyme
stabilizers, complexing agents for heavy metals, for example amino
polycarboxylic acids, amino hydroxyl polycarboxylic acids,
polyphosphonic acids and/or amino polyphosphonic acids, foam
inhibitors, for example organopolysiloxanes or paraffins, solvents
and optical brighteners, for example stilbene disulfonic acid
derivatives. Optical brighteners, in particular compounds from the
class of substituted
4,4'-bis-(2,4,6-triamino-s-triazinyl)-stilbene-2,2'-disulfonic
acids, up to 5 wt. %, in particular 0.1 wt. % to 2 wt. %, of
complexing agents for heavy metals, in particular aminoalkylene
phosphonic acids and salts thereof, and up to 2 wt. %, in
particular 0.1 wt. % to 1 wt. %, of foam inhibitors are preferably
contained in products that contain an active ingredient used in
accordance with the invention, wherein the specified proportions by
weight relate in each case to total product.
[0033] In addition to water, solvents which in particular can be
used in the case of liquid products are preferably those which can
be mixed with water. These include the lower alcohols, for example
ethanol, propanol, isopropanol, and the isomeric butanols,
glycerol, lower glycols, for example ethylene and propylene glycol,
and the ethers derivable from the specified compound classes. The
active ingredients used in accordance with the invention are
generally present in such liquid products in dissolved or suspended
form.
[0034] Enzymes, which are present optionally, are preferably
selected from the group comprising proteases, amylases, lipases,
cellulases, hemicellulases, oxidases, peroxidases, pectinases and
mixtures thereof. Proteases obtained from microorganisms such as
bacteria or fungi are primarily considered. They can be obtained
from suitable microorganisms by fermentation processes, as is
known. Proteases are commercially obtainable for example under the
names BLAP.RTM., Savinase.RTM., Esperase.RTM., Maxatase.RTM.,
Optimase.RTM., Alcalase.RTM., Durazym.RTM. or Maxapem.RTM.. The
usable lipases can be obtained for example from Humicola
lanuginosa, from Bacillus types, from Pseudomonas types, from
Fusarium types, from Rhizopus types, or from Aspergillus types.
Suitable lipases are commercially obtainable for example under the
names Lipolase.RTM., Lipozym.RTM., Lipomax.RTM., Lipex.RTM.,
Amano.RTM. lipase, Toyo-Jozo.RTM. lipase, Meito.RTM. lipase and
Diosynth.RTM. lipase. Suitable amylases are commercially available
for example under the names Maxamyl.RTM., Termamyl.RTM.,
Duramyl.RTM. and Purafect.RTM. OxAm. The usable cellulases can be
an enzyme obtainable from bacteria or fungi, which enzyme has a pH
optimum preferably in the weakly acidic to weakly alkaline range
from 6 to 9.5. Cellulases of this type are commercially obtainable
under the names Celluzyme.RTM., Carezyme.RTM. and
Ecostone.RTM..
[0035] The conventional enzyme stabilizers optionally present, in
particular in liquid products, include amino alcohols, for example
mono-, di-, triethanol and -propanol amine and mixtures thereof,
lower carboxylic acids, boric acid, alkali borates, boric
acid-carboxylic acid combinations, boric acid esters, boric acid
derivatives, calcium salts, for example Ca-formic acid combination,
magnesium salts, and/or sulfur-containing reducing agents.
[0036] Suitable foam inhibitors include long-chain soaps, in
particular behenic soaps, fatty acid amides, paraffins, waxes,
microcrystalline waxes, organopolysiloxanes, and mixtures thereof,
which additionally can contain micro-fine, optionally silanized or
otherwise waterproofed silica. Foam inhibitors of this type are
preferably bound to granular, water-soluble carrier substances for
use in particulate products.
[0037] In a further preferred embodiment a product in which the
active ingredient to be used in accordance with the invention is
incorporated is provided in the form of particles and contains up
to 25 wt. %, in particular 5 wt. % to 20 wt. % of bleaching agent,
in particular alkali percarbonate, up to 15 wt. %, in particular 1
wt. % to 10 wt. % of bleach activator, 20 wt. % to 55 wt. % of
inorganic builder, up to 10 wt. %, in particular 2 wt. % to 8 wt. %
of water-soluble organic builder, 10 wt. % to 25 wt. % of synthetic
anionic surfactant, 1 wt. % to 5 wt. % of non-ionic surfactant, and
up to 25 wt. %, in particular 0.1 wt. % to 25 wt. % of inorganic
salts, in particular alkali carbonate and/or alkali hydrogen
carbonate.
[0038] In a further preferred embodiment a product in which the
active ingredient to be used in accordance with the invention is
incorporated is liquid and contains 1 wt. % to 25 wt. %, in
particular 5 wt. % to 15 wt. % of non-ionic surfactant, up to 10
wt. %, in particular 0.5 wt. % to 8 wt. % of synthetic anionic
surfactant, 3 wt. % to 15 wt. %, in particular 5 wt. % to 10 wt. %
of soap, 0.5 wt. % to 5 wt. %, in particular 1 wt. % to 4 wt. % of
organic builder, in particular polycarboxylate such as citrate, up
to 1.5 wt. %, in particular 0.1 wt. % to 1 wt. % of complexing
agent for heavy metals, such as phosphonate, and additionally
optionally contained enzyme, enzyme stabilizer, dye and/or
fragrance, water and/or water-miscible solvent.
DETAILED DESCRIPTION OF THE INVENTION
[0039] The use of a combination of a soil release active ingredient
essential to the invention with a soil release polymer formed from
a dicarboxylic acid and a potentially polymeric diol to enhance the
cleaning performance of detergents during the laundering of
textiles is also possible. Such combinations with a polymer which
in particular is a polyester-active dirt release polymer are also
possible within the scope of products according to the invention
and the method according to the invention.
[0040] The known polyester-active soil release polymers, which can
be used in addition to the active ingredients essential to the
invention, include copolyesters of dicarboxylic acids, for example
adipic acid, phthalic acid or terephthalic acid, diols, for example
ethylene glycol or propylene glycol, and polydiols, for example
polyethylene glycol or polypropylene glycol. The soil release
polymers that are used with preference include compounds which are
formally accessible by esterification of two monomer parts, wherein
the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the
second monomer is a diol HO--(CHR.sup.11--).sub.aOH, which can also
be present in the form of a polymeric diol
H--(O--(CHR.sup.11).sub.a).sub.bOH. Therein, Ph means an o-, m- or
p-phenyl group, which can carry 1 to 4 substituents, selected from
alkyl groups having 1 to 22 C atoms, sulfonic acid groups, carboxyl
groups, and mixtures thereof, R.sup.11 is hydrogen, an alkyl group
having 1 to 22 C atoms and mixtures thereof, a is a number from 2
to 6, and b is a number from 1 to 300. In the polyesters obtainable
therefrom, there are preferably present both monomer diol units
--O--(CHR.sup.11--).sub.aO-- and polymer diol units
--(O--(CHR.sup.11--).sub.a).sub.bO--. The molar ratio of monomer
diol units to polymer diol units is preferably 100:1 to 1:100, in
particular 10:1 to 1:10. In the polymer diol units, the degree of
polymerization b preferably lies in a range of from 4 to 200, in
particular from 12 to 140. The molecular weight or the mean
molecular weight or the maximum of the molecular weight
distribution of preferred soil release polyesters lies in a range
of from 250 g/mol to 100,000 g/mol, in particular from 500 g/mol to
50,000 g/mol. The acid forming the basis of the group Ph is
preferably selected from terephthalic acid, isophthalic acid,
phthalic acid, trimellitic acid, mellitic acid, the isomers of
sulfophthalic acid, sulfoisophthalic acid, and sulfoterephthalic
acid and mixtures thereof. Provided the acid groups thereof are not
part of the ester bonds in the polymer, they are preferably present
in salt form, in particular as alkali salt or ammonium salt.
[0041] Among these, the sodium and potassium salts are particularly
preferred. If desired, small proportions, in particular no more
than 10 mol % in relation to the proportion of Ph with the
above-mentioned meaning, of other acids comprising at least two
carboxyl groups, can be contained in the soil release polyester
instead of the monomer HOOC-Ph-COOH. These other acids for example
include alkylene and alkenyl dicarboxylic acids, such as malonic
acid, succinic acid, fumaric acid, maleic acid, glutaric acid,
adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic
acid. The preferred diols HO--(CHR.sup.11--).sub.aOH include those
in which R.sup.11 is hydrogen and a is a number from 2 to 6, and
those in which a has the value 2 and R.sup.11 is selected from
hydrogen and the alkyl groups having 1 to 10, in particular 1 to 3
C atoms. Among the last-mentioned diols, those of formula
HO--CH.sub.2--CHR.sup.11--OH, in which R.sup.11 has the
above-mentioned meaning, are particularly preferred. Examples of
diol components are ethylene glycol, 1,2-propylene glycol,
1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1,2-dodecanediol
and neopentyl glycol. Among the polymeric diols, polyethylene
glycol having a mean molar mass ranging from 1,000 g/mol to 6,000
g/mol is particularly preferred.
[0042] If desired, these polyesters composed as described above can
also be end-group-terminated, wherein alkyl groups having 1 to 22 C
atoms and esters of monocarboxylic acids are potential end groups.
The end groups bound via ester bonds can be based on alkyl, alkenyl
and aryl monocarboxylic acids having 5 to 32 C atoms, in particular
5 to 18 C atoms. These include valeric acid, caproic acid, enanthic
acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid,
undecenoic acid, lauric acid, lauroleic acid, tridecanoic acid,
myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid,
stearic acid, petroselinic acid, petroselaidic acid, oleic acid,
linoleic acid, linolaidic acid, linolenic acid, elaostearic acid,
arachinic acid, gadoleic acid, arachidonic acid, behenic acid,
erucic acid, brasidinic acid, clupanodonic acid, lignoceric acid,
cerotic acid, melissic acid, benzoic acid, which can carry 1 to 5
substituents with a total of up to 25 C atoms, in particular 1 to
12 C atoms, for example tert.-butylbenzoic acid. The end groups can
also be based on hydroxymonocarboxylic acids having 5 to 22 C
atoms, including for example hydroxyvaleric acid, hydroxycaproic
acid, ricolinic acid, the hydrogenation product thereof
hydroxystearic acid, and o-, m- and p-hydroxybenzoic acid. The
hydroxymonocarbxylic acids can in turn be bound to one another via
their hydroxyl group and their carboxyl group and thus can be
present multiple times in an end group. The number of
hydroxymonocarboxylic acid units per end group, i.e. their degree
of oligomerization, preferably lies in the range of from 1 to 50,
in particular from 1 to 10. In a preferred embodiment of the
invention, polymers formed of ethylene terephthalate and
polyethylene oxide terephthalate, in which the polyethylene glycol
units have molecular weights of from 750 g/mol to 5,000 g/mol and
the molar ratio of ethylene terephthalate to polyethylene oxide
terephthalate is 50:50 to 90:10, are used in combination with an
active ingredient essential to the invention.
[0043] The polyester-active soil release polymers are preferably
water-soluble, wherein the term "water-soluble" shall be understood
to mean a solubility of at least 0.01 g, preferably at least 0.1 g
of the polymer per liter of water at room temperature, and pH 8.
Polymers used with preference, however, have a solubility of at
least 1 g per liter, in particular at least 10 g per liter, under
these conditions.
[0044] Preferred laundry aftertreatment agents that contain an
active ingredient to be used in accordance with the invention
comprise what is known as an esterquat as laundry-softening active
ingredient, in other words a quaternized ester from carboxylic acid
and amino alcohol. These are known substances that can be obtained
in accordance with the relevant preparatory methods known within
the field of organic chemistry, for example by partially
esterifying triethanolamine in the presence of hypophosphorous acid
with fatty acids, passing air through, and then quaternizing with
dimethyl sulfate or ethylene oxide. The production of solid
esterquats is also known, in which case the quaternization of
triethanol amine esters is performed in the presence of suitable
dispersants, preferably fatty alcohols.
[0045] Preferred esterquats in the products are quaternized fatty
acid triethanolamine ester salts of the following formula (IV)
##STR00004##
in which R.sup.1CO stands for an acyl group having 6 to 22 carbon
atoms, R.sup.2 and R.sup.3, independently of one another, stand for
hydrogen or R.sup.1CO, R.sup.4 stands for an alkyl group having 1
to 4 carbon atoms or a (CH.sub.2CH.sub.2O).sub.qH group, m, n and p
in total stand for 0 or numbers from 1 to 12, q stands for numbers
from 1 to 12, and X stands for a charge-balancing anion, such as
halide, alkyl sulfate or alkyl phosphate. Typical examples of
esterquats that can be used within the sense of the invention are
products based on caproic acid, caprylic acid, capric acid, lauric
acid, myristic acid, isostearic acid, stearic acid, oleic acid,
elaidic acid, arachinic acid, behenic acid and erucic acid and
technical mixtures thereof, as are produced for example with the
high-pressure splitting of natural fats and oils. Industrial
C.sub.12/18 coconut fatty acids and in particular partially
hardened C.sub.16/18 tallow or palm fatty acids and C.sub.16/18
fatty acid cuts rich in elaidic acid are preferably used. In order
to produce the quaternized esters, the fatty acids and the
triethanolamine can be used generally in a molar ratio from 1.1:1
to 3:1. In view of the application properties of the esterquats, a
ratio for use of from 1.2:1 to 2.2:1, preferably 1.5:1 to 1.9:1,
has proven to be particularly advantageous. The esterquats used
with preference are technical mixtures of mono-, di- and triesters
with an average degree of esterification of from 1.5 to 1.9 and
derive from industrial C.sub.16/18 tallow or palm fatty acid
(iodine value 0 to 40). Quaternized fatty acid triethanolamine
ester salts of formula (IV), in which R.sup.1CO stands for an acyl
group having 16 to 18 carbon atoms, R.sup.2 stands for R.sup.1CO,
R.sup.3 stands for hydrogen, R.sup.4 stands for a methyl group, m,
n and p stand for 0, and X stands for methyl sulfate, have proven
to be particularly advantageous.
[0046] Besides the quaternized carboxylic acid triethanolamine
ester salts, quaternized ester salts of carboxylic acids with
diethanol alkyl amines of formula (V) can also be considered as
esterquats
##STR00005##
in which R.sup.1CO stands for an acyl group having 6 to 22 carbon
atoms, R.sup.2 stands for hydrogen, or R.sup.1CO, R.sup.4 and
R.sup.5, independently of one another, stand for alkyl groups
having 1 to 4 carbon atoms, m and n in total stand for 0 or numbers
from 1 to 12, and X stands for a charge-balancing anion, such as
halide, alkyl sulfate or alkyl phosphate.
[0047] Lastly, a further group of suitable esterquats is
constituted by the quaternized ester salts of carboxylic acids with
1,2-dihydroxypropyldialkyl amines of formula (VI)
##STR00006##
in which R.sup.1CO stands for an acyl group having 6 to 22 carbon
atoms, R.sup.2 stands for hydrogen, or R.sup.1CO, R.sup.4, R.sup.6
and R.sup.7, independently of one another, stand for alkyl groups
having 1 to 4 carbon atoms, m and n in total stand for 0 or numbers
from 1 to 12, and X stands for a charge-balancing anion, such as
halide, alkyl sulfate or alkyl phosphate.
[0048] With regard to the selection of preferred fatty acids and
the optimal degree of esterification, the details provided by way
of example for (IV) also apply similarly for the esterquats of
formulas (V) and (VI). The esterquats are usually commercially
available in the form of 50 to 90 wt. % alcoholic solutions, which
can also be diluted with water without difficulty, with ethanol,
propanol and isopropanol being the usual alcoholic solvents.
[0049] Esterquats are preferably used in amounts of from 5 wt. % to
25 wt. %, in particular 8 wt. % to 20 wt. %, in each case in
relation to the total laundry aftertreatment agent. If desired, the
laundry aftertreatment agents used in accordance with the invention
can additionally contain detergent ingredients as described above,
provided they do not unreasonably interact negatively with the
esterquat. A liquid, water-containing agent is preferred.
EXAMPLES
Example 1: Production of 6-desoxy-6-amino-cellulases
a) Synthesis of .omega.-Methoxyethylamino Cellulose (Active
Ingredient I)
[0050] 50 g of tosyl cellulose (185 mmol), dissolved in 1 L DMSO
were mixed, under stirring, with 50 mL 2-methoxyethylamine (575
mmol). The reaction solution was heated to 100.degree. C. and,
after a reaction time of 6 h, the product precipitated in 6 L of
2-propanol and the precipitate was removed by means of a G3 frit.
The solid was washed three times with 1.5 L of 2-propanol. The
product was then dissolved in 1 L of distilled water. The solution
was freed from residues of 2-propanol by azeotropic distillation at
80 mbar. The solution was then mixed with the anion exchanger
IRA-410 (Cl form) and stirred at room temperature for 18 h. The
anion exchanger was filtered off, and the aqueous solution was
lyophilized (8 days, -55 OC, 0.36 mbar).
[0051] Yield: 28 g (72%)
[0052] FT-IR (KBr): 3412 cm.sup.-1 v (OH) 2894 cm.sup.-1 v (CH)
1646 cm.sup.-1 v (N--H) 1597 cm.sup.-1 v (C.dbd.C) 1456 cm.sup.-1 v
(CH.sub.2/CH.sub.3) 1366 cm.sup.-1 v.sub.as (SO.sub.2) 1160
cm.sup.-1 v.sub.s (SO.sub.2) 1069 cm.sup.-1 v (C--O--C)
[0053] 1H-NMR [DMSO-d.sub.6, 250 MHz]: 7.77 ppm-7.42 ppm
(H.sub.arom,t) 5.38 ppm-3.76 ppm (H1-H6 and OH) 3.38 ppm
(OCH.sub.3) 3.05 ppm (CH.sub.2) 2.70 ppm (CH.sub.2) 2.40 ppm
(CH.sub.3,t)
[0054] .sup.13C-NMR [DMSO-d.sub.6, 250 MHz]: 130.0 ppm (C--H.sub.m)
128.2 ppm (C--H.sub.o) 103.0 ppm (C-1) 100.9 ppm (C-1') 82.4 ppm
80.8 ppm 75.2 ppm 73.6 ppm (C-2-C-5) 71.8 ppm 71.5 ppm (CH.sub.2)
60.6 ppm (C-6) 58.4 ppm (OCH.sub.3) 49.7 ppm 48.8 ppm (CH.sub.2)
21.6 ppm (CH.sub.3,t)
[0055] Elemental analysis: C, 44.60% H, 6.83% N, 3.39% S, 1.33%
[0056] DS.sub.EA,tosyl: 0.08 D.sub.SE, amine: 0.49
b) Synthesis of .omega.-Methoxyethyl Methyl Amino Cellulose (Active
Ingredient II)
[0057] 50 g of tosyl cellulose (180 mmol) were dissolved in 850 mL
DMSO. 59.8 mL of 2-methoxyethylmethylamine (550 mmol) were added to
the clear solution. The reaction solution was stirred for 6 h at
100.degree. C. The product was then precipitated in 7 L of acetone.
The solid was separated over a G3 frit and washed 3 times with 1.5
L acetone. Once the product had dissolved in 1 L of distilled
water, solvent residues were removed by azeotropic distillation at
80 mbar. The anion exchanger IRA-410 (Cl form) was then added, and
the mixture was stirred at room temperature for 18 h. The anion
exchanger was filtered off, and the aqueous solution was
lyophilized (6 days, -55.degree. C., 0.36 mbar).
[0058] Yield: 20 g (54%)
[0059] FT-IR: 3325 cm.sup.-1 v (OH) 2880 cm.sup.-1 v (CH) 1638
cm.sup.-1 v (N--H) 1455 cm.sup.-1 v (CH.sub.2/CH.sub.3) 1363
cm.sup.-1 v.sub.as (SO.sub.2) 1061 cm.sup.-1 v (C--O--C)
[0060] .sup.1H-NMR [DMSO-d.sub.6, 250 MHz]: 7.78 ppm-7.44 ppm
(H.sub.arom,t) 5.42 ppm-3.78 ppm (H1-H6 and OH) 3.37 ppm
(OCH.sub.3) 3.07 ppm (CH.sub.2) 2.66 ppm (CH.sub.2) 2.31 ppm
(CH.sub.3)
[0061] .sup.13C-NMR [DMSO-d.sub.6, 250 MHz]: 129.6 ppm (C--H.sub.m)
127.7 ppm (C--H.sub.o) 102.6 ppm (C-1') 79.4 ppm 74.7 ppm 73.2 ppm
72.2 ppm (C-2-C-5) 69.7 ppm (CH.sub.2) 59.9 ppm (C-6.sub.t) 58.0
ppm (OCH.sub.3) 56.5 ppm (CH.sub.2) 42.9 ppm (CH.sub.3) 21.1 ppm
(CH.sub.3,t)
[0062] Elemental analysis: C, 39.09% H, 5.85% N, 2.47% S, 0.92%
[0063] DS.sub.EA,tosyl: 0.06 DS.sub.EA,amine: 0.34
Example 2: Product
[0064] Table 1 shows the composition (ingredients in wt. %, in each
case in relation to the product as a whole) of the detergents M1,
M2 and M3 according to the invention and of the product VI free
from a corresponding active ingredient:
TABLE-US-00001 TABLE 1 Composition V1 M1 M2 M3 C.sub.9-13
alkylbenzene sulfonate, Na salt 6 6 6 6 Sodium lauryl ether sulfate
with 2 EO 8 8 8 8 C.sub.12-14 fatty alcohol with 7 EO 6 6 6 6
C.sub.12-18 fatty acid, Na salt 3 3 3 3 NaOH 2 2 2 2 Citric acid 2
2 2 2 1-hydroxyethan-1, 1-diphosphonate, 0.2 0.2 0.2 0.2 Na salt
Enzyme, dye, opt. brightener, alcohols, 5 5 5 5 boric acid Active
ingredient l.sup.a) -- 1 1.5 -- Active ingredient ll.sup.b) -- --
-- 1.5 Water to 100 .sup.a)From example 1a; R.sup.1 = H and R.sup.2
= methoxyethyl with DS.sub.amine = 0.49 and DS.sub.tosyl =0.08
.sup.b)From example 1b; R.sup.1 = methyl and R.sup.2 = methoxyethyl
with DS.sub.amine = 0.34 and DS.sub.tosyl = 0.06
Example 3: Graying
[0065] The products V1 or M1 were tested in a Miele.RTM. W 1714
washing machine (cotton washing program, 40.degree. C.; water
hardness 16.degree. dH; standardized dirt carrier; dosing 70 g of
the particular product per washing cycle). Besides a full laundry
load of 3.5 kg, the materials specified in the table (in each case
8 textile pieces measuring 20.times.40 cm) were also used.
[0066] The brightness values (Y values) of the materials after 3
washes under the specified conditions with the particular product
are specified in Table 2.
TABLE-US-00002 TABLE 2 Brightness values Textile/Product V1 M1 WFK
10A 77.0 78.1 WFK 12A terry cloth 70.5 73.6 EMPA 221 77.2 78.3
T-Shirt (100% cotton) 76.3 77.4
[0067] It can be seen that, with use of the product according to
the invention, the materials gray to a lesser extent than with use
of the product not containing the active ingredient essential to
the invention.
Example 4
[0068] Clean textiles made of polyester (for stains A to E) or
cotton (for stains F to H) were washed 3 times in a Miele.RTM. W
1514 washing machine at 40.degree. C. in each case with 17 L of
water of 16.degree. dH per washing cycle with the detergent V1
specified in Example 2 or with the detergent M2 or M3 likewise
specified there, in a dosing of, in each case, 4.1 g/L of washing
lye, and were then air-dried. Standardized stains (A: dust/sebum;
B: black shoe polish; C: engine oil; D: lard; E: lipstick; F:
make-up; G: lard; mascara) were then applied to the test textiles,
and the stains were aged for 7 days. The textiles prepared in this
way were washed again with the detergent under the above-mentioned
conditions at a laundry load of 3.5 kg (clean laundry plus test
textiles). The assessment was performed by calorimetry; the mean
values of the differences between the brightness values before and
after washing between the products M2 or M3 and V1 (MY values) from
6 tests are stated in Table 2.
TABLE-US-00003 TABLE 2 Brightness differences .DELTA..DELTA.Y
Stain/product M2 M3 A 8.3 11.2 B 17.0 13.7 C 4.9 3.9 D 2.4 2.4 E
5.1 5.5 F 6.5 5.7 G 3.1 n.b. H n.b. 6.4 n.b. not determined
* * * * *